Substituted dioxanes



Patented Oct 31, 1944 ,ttiASt mouse sunsn'ro'mn moms .Henry C. Chitwooll, Charleston, W. Va., assignor to Carbide and Carbon Chemicals Corporation, a corporation of New York No Drawing. ApplicationJune 17, 1942,

- SerialNo.447,453

12 Claims. (01. 26(1-338) This invention relates to a new class of dig yo a-l, as desc ed in e pp o of oxane derivatives and to a process for preparing Dowell and McNamee, Serial No. 383,929, filed them. A March 18, 1941.

Although the synthesis of diethers of dihya 11' from 2 to 7 mols of the alcohol per mol of droxydioxane, such as the dialkoxydioxanes, by slyoxal are employed. the for on of e te the condensation of dichlordioxane with alcohols substituted dioxanes will be favored. The foris known, the preparation of the tetraethers of m tion Of' t se latter o po n y be tetrahydroxydioxanes has not heretofore been counted for by several hypotheses, although the known. These latter compounds contain at least mec of the t o Which 0001118 in the six oxygen atoms in ether linkagesand are pow- 10 formation of these substituted dloxanes is not e'rful solvents for oils, waxes, resins, and celluown o t It 18 possible that the glyoxal lose derivatives. and alcohol first react to form a glyoxal di-hemi- The tetraethers of tetrallydroxydioxane are obta wh c enses W itself to yield the tained by condensingglyoxal with a monohydric tetra-alkoxydioxane according to the following alcohol according to the process herein described. sc

Since glyoxal is more readily obtainable in asso- 2 411011 2OHC-CHO 2R0 cmomcmomon elation with water than as monomeric glyoxal,

the invention will be described with reference to Aloohol Glyoxal Glyoxal djlhemiacem this source of glyoxal. Glyoxal forms a hydrate (3) OH HO 0 1211 gatigr, agiighe exact constitution of this go goofi ho-oa RO-C hc-oR +23 0 o 2 siirrngest hyxoates own. It is probable that the B0 H H g gg (3H0 and CH-(OH): 0H o CHOH), -Glyoxal di-homiacetal Tetraether of Water 25 v tetrahydroxydioxane are in q ium wit c cl c polyme c hydrates On the other hand, it is possible that the alcoe formation of t ese po me ic hyd a es a hol condenses with the tetrahydroxydioxane form involve the elimination of part of the water asf th 1 oxal drate in the I llowin meme 1 sociated with the hydrate as follows: 0 8y by 0 g r o 1 CH0 0 2'5 4 Ire-ch hc-on H0 g 4ROH 110- H H -on Glyoxal Water \O/ I Totrahydroxydimne Alcohol llmoma no-c nc-on mo 5 Y 0 I more: Ho- H n --on E0413 0 +iH|O Gl oxal Ttrah dro -di Q R0 {I E04,}; hygmte e y xy oxane 4o 7 o As more water is removed, further polymeriza- 1 Tetmthe Water tion of the cyclic hydrates may occur. tiamhydmydmme w a monohydric alcohol-1s added to Such Whatever reaction mechanism may account for a system, glyoxal hemi-acetals the formation of the tetraethers of tetrahydroxy- 0H HO OH dioxane, the following .over-all equation may be written: OCHHC\ and /CH-HC 0 on no I OR one I RO-Kl hc-on are initially formed, where R is the residue or the l H H 0B monohydric alcohol. Upon heating such mix- H 110- tureswith removal of water, glyoxal tetra-acet'als 0 m formed by further acetalizatlon of these Glyoxal Alcohol Tetraether or Water r-aoetals. Favorable conditions for this remhydrotydioxane action include the use of a large excess of alcohol, Although a mixture of acetals will probably for instance, 8 to 10 mols of alcohol per mol of be obtained in anycase, the formation of the 4 of water per mol of glyoxal, in addition to the use of the proper molar ratio of alcohol to glyoxal. In any event, the condensation is discontinued before 2 mols of water per mol of glyoxal have been split out in the condensation, in order to prevent the formation of preponderant quantitles of the'glyoxal tetra-acetals. Where glyoxal hydrates, polymers, hydrated polymers, or dehydrated polymeric hydrates of glyoxal are involved, the molar ratios specified are based on the aldehyde reactivity of these glyoxal equivalents, calculated as monomeric glyoxal. Furthermore, these molar ratios are based on the amount of material within the. reaction zone, and

the replenishment of unreacted alcohol which has distilled over with the water is not considered to increase the total ratio of alcohol to glyoxal in the reaction.

The reaction is preferably carried -out with moderate heating of the reactants in the pres- The practice of the invention may be shown by the following examples:

Example '1- Six hundred and fifty-five (655) grams of a 49.6% aqueous solution of glyoxal (containing 5.6 mols of glyoxal in the form of its, hydrate) were evaporated under reduced pressure until a swollen, amorphous solid was obtained. This solid represents a dehydrated polymeric hydrate of glyoxal. To this solid was added 1425 grams (31 mols) of ethanol, 05 c. c. of concentrated sulfuric acid. as a catalyst, and 250 c. c. of benzene. The mixture was placed in a flask having a distillation column and heated under reflux.

The water formed wasremoved as an azeotropic distillate with benzene. Upon distilling the reaction .products, a 31% yield of a liquid identified as tetraethoxydioxane wasobtained. In addition, glyoxal tetraethyl acetal and glyoxal semidiethyl acetal wereobtained. Tetraethoxydioxenceof an acid catalyst, such as sulfuric acid. The water of reaction may be removed as an azeotropic distillate with an inert, volatile liquid, such as benzene, toluene, xylene or diisopropyl ether. The water may also be removed by distillation of the reactants under a vacuum. When the theoretical amount of water has been re moved, the catalyst is neutralized and the products separated by distillation The by-products which may be formed in the reaction, such as glyoxal diacetals and glyoxal tetra-acetals, as well as any high-boiling complex acetals, may be reacted with additional al-.'

cohol in the presence of an acidcatalyst to increase the yield of tetra-substituted dioxaneso These acetals may serve as a source of glyoxal ane boils at 114 to 117 C. at 6 mm., possesses a specific gravity of 1.036 at 20 C., and has a refractive index of 1.4243 at 20 C. The molecular refraction calculated from the density and refractive index is 65.3, whereas the theoretical value for the bonds in tetraethoxydioxane is Example 2 A'mixture of 1309 grams of 49.5%aqueous glyoxal (11.16 mols), 2300 -grams of ethanol through hydrolysis in such reprocessing, or an acetal interchange may occur towards the forma-,

tion of the most stable acetal. V I

The reaction is applicable to both aliphatic and aromatic alcohols, and in one case, tetraalkoxydioxanes are formed, and in the other,

tetra-aralkoxydioxanes result. Examples of suitable aliphatic monohydric alcohols include methanol, ethanol, isopropanol, butanol, tertiary 'butyl alcohol and chlorethyl and chlorisopropyl alcohol, as well as higher aliphatic alcohols, such as n-hexyl, Z-ethyl butyl, heptyl, n-octyl, and 2- ethyl hexyl alcohols. Unsaturated alcohols, such as ally] and crotyl alcohols may also be used. Alcohol-others, such as methoxy-ethanol, ethoxyethanol and butoxyethanol may be employed to form even more highly etherifled products. Suit able aromaticalcohols include benzyl alcohol, phenyl ethyl carbinol, phenyl ethyl alcohol, and cinnamyl alcohol. Cyclic alcohols, such as cyclohexanol and cyclopentanol, and 'heterocyclic alcohols. such as furfuryl alcohol may also be employed. It is to beunderstood that the invention is not limited to alcohols having hydrocarbon groups attached to the hydroxyl group, and alcohols which contain substituents in the radicals attached to the hydroxyl groups are included within the scope of the invention, provided that the hydroxyl group in such compounds is alcoholic.

The invention is of broad scope as to the tetraethers of tetrahydroxydioxane with monohydric mols) 500 c. c. of benzene and 2 ,c. c. of concentrated sulfuric acid was refluxed in a still fitted with a decanter. The lower layer of the distillate containing alcohol and water wasremoved and the top layer returned to the column. After 23 hours, 1400 grams of the lower layer had been.

decanted. A fresh portion of ethanol (1000 grams) was added and the refluxing was continued for 9 hours. By this time the lower layer was forming in the distillate very slowly. The

Y benzene and excess ethanol were then distilled ofi'at atmospheric pressure until a kettle temperature of 150 C. was reached. The distillation was then continued under vacuum. Three products distilled and were approximately separatedinto these fractions: 59 grams boiling at 40 to C. at 10 mm. of mercury absolute pressure, 79 grams boiling at 65 C. at.10

to at 5 mm., and 164 grams boiling at 100 to C. at 5 mm. These three fractions consisted principally of glyoxal diethyl acetal, glyoxal tetraethyl 'acetal, and tetraethoxydioxane, res ectively. The respective yields were 5.4%, 3.4%, and 11.2%. The remaining 80%.of the original glyoxal was in the form of complex hi her acetals which were left in the kettle as a large residue.

The ability to increase the yield of desired product by acetal interchange was demonstrated I by the following experimentf alcohols. This group is claimed as an entirely The glyoxal diethyl acetal and glyoxal tetraethyl acetal cuts from the previous experiment were added to the kettle residue of high boiling acetals. 'Sixteen hundred and seventy (1670) erams of ethanol, 500 c. c. of benzene and l c. c. of concentrated sulfuric acid were added. The

mixture was refluxed for 45 hours, during which time 300 grams of the lower layer. of the distillate were decanted. The product was fract onated as before. The amounts of glyoxal diethyl acetal. glyoxal tetraethyl acetal, and tetraethoxydioxane obtained corresponded to yields of 6.6%, 26.8%, and 30.5% respectively, based on the glyoxal originally used. The total yield of tetraethoxydioxane was thus increased to 41.7% of the theoretical value. A residue of only 257 grams. of high-boiling acetals remained, corresponding to about 23% of the original glyoxal.

By additional reprocessing of this residue and of the lower boiling products, the yield of tetraethoinrdioxane may be further increased.

Example 3 7 An experiment similar to that in Example 1 was conducted with isopropyl alcohol instead of ethanol. In addition to the diand tetraisopropyl acetals of glyoxal there was obtained a substantial amount of a compound boiling at 100 C. at 1.2 mm. mercury to 115 C. at 1.6 mm. Its refractive index was 1.4238 at 20 C. and its specific gravity was 0.976 at 20 C. It was identifled by its molecular weight and molecular refraction as tetraisopropoxydioxane. (Molecular weight found by Menzies-Wright method, 324.6;

theoretical, 320.4. Molecular refraction calcu-- equivalents which react like glyoxal, such as the hydrates, polymers, hydrated polymers, and dehydrated polymeric hydrates of glyoxal.

I claim: 1. As new chemical compounds, 2,3,5,6-tetraethers of tetrahydroxydioxane with monohydric alcohols.

2. As new chemical compounds, 2,3;5,6-tetraaralkoxydioxanes.

3. As new chemical compounds, 2,3,5,6-tetraalkoxydioxanes.

which comprises condensing glyoxal with an aliphatic monohydric alcohol, removing water from the zone of reaction during the condensation, continuing the condensation until about one mol of .water per mol of glyoxal has been split out, and recovering a 2,3,5,6-tetra-alkoxydioxane from the reaction products. I

9. Process for making tetra-alkoxydioxanes which comprises condensing glyoxal with an aliphatic monohydric alcohol in the presence of an acid catalyst and a volatile aromatic hydrocarbon, distilling water from the zone of reaction during the condensation as an azeotropic distillate with said volatile aromatic hydrocarhen, the molar ratio of alcohol to glyoxal being at least 2 to 1, and not greater than 7 to 1, continuing the condensation until substantially less 1 than two mols of water per mol of glyoxal have been split out, and recovering a 2,3,5,6-tetraalkoxydioxane from the reaction products.

10. Process for making 2,3,5,6-tetraethers of tetrahydroxydioxane with monohydric alcohols which comprises condensing glyoxal with a monohydric alcohol, removing water from the zone of reaction during the condensation, continuing the condensation until substantially less than two mols of water per mol of glyoxal have been split out, thereafter separating said tetra-v ethers from other acetal products of the reaction, and heating these acetal products with 1 additional amounts of the monohydric alcohol 4. As -a new chemical compound, 2,3,5,6-

6. Process for making. tetraethers oi tetraaction during the condensation, the molar ratio of alcohol to glyoxal being at least 2 to 1 and in the presence of an acid catalyst to form additional amo'unts of said tetraethers, and recovering said tetraethers from the reaction products.

11. Process for making 2,3,5,6-tetraethoxydioxane which comprises condensing glyoxal with ethanol, removing water from the zone of 'reaction during the condensation, continuing the condensation until substantially less than two mols of water per mol of glyoxal have been split out, and recovering said tetr'aethoxydioxane from the reaction products.

12 Process for making 2,3,5,6-tetraisopropoxy- 'dioxane which comprises condensing. glyoxal with isopropanol, removing water from the zone of reaction during the condensation, continuing .the condensation until substantially less than two mols of water per mol of glyoxal have been split out, and recovering said tetraisopropoxydioxane from the reaction products.

HENRY C. CHITWOOD.

Patent Nb; 2,361,456.

Certificate of Correction 4 October 31, 1944. HENRY O. CHITWGOD i It is hereby certified that errors appesr in the rinted speoificationof theabove numbered patent requiring correction as follows: age 1, second column, lines 35 to 40, for

no-o Eo-on o no-cfi -c'-on o noa 30-01: Ito-$11 HA-OR {age 3, first column, line 49, for th'e'words mol or read mol of; and that theisaid;

otters Patent should be read with these corrections therein that the same-may conform to the record of the case in the Patent Oflice.

Signed and sealed this 23rd day of January, A; D. 1945.

LESLIE FRA ER, 1

Acting Commissioner of Patents. 

